WO2023276864A1 - Composé silsesquioxane, et procédé de fabrication de celui-ci - Google Patents

Composé silsesquioxane, et procédé de fabrication de celui-ci Download PDF

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WO2023276864A1
WO2023276864A1 PCT/JP2022/025227 JP2022025227W WO2023276864A1 WO 2023276864 A1 WO2023276864 A1 WO 2023276864A1 JP 2022025227 W JP2022025227 W JP 2022025227W WO 2023276864 A1 WO2023276864 A1 WO 2023276864A1
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group
carbon atoms
hydrocarbon group
acid
thiol
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PCT/JP2022/025227
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Japanese (ja)
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正幸 横山
哲雄 奥山
郷司 前田
洋行 涌井
直樹 渡辺
公洋 松川
建介 中
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東洋紡株式会社
国立大学法人京都工芸繊維大学
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Publication of WO2023276864A1 publication Critical patent/WO2023276864A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur

Definitions

  • the present invention relates to a novel silsesquioxane compound having a dicarboxylic anhydride group and a method for producing the same, and is useful as a raw material for producing polyimide films.
  • Polyimide film has excellent heat resistance and good mechanical properties, and is widely used in the electrical and electronic fields as a flexible material. However, since a general polyimide film is colored yellowish brown, it cannot be applied to parts such as display devices that require light transmission.
  • the colored polyimide film cannot be used as a substrate material for a liquid crystal display that displays images by turning light transmission on and off. , the rear side of a reflective display system or a self-luminous display device.
  • Patent Documents 1 to 3 there are attempts to develop colorless and transparent polyimide films using fluorinated polyimide resins, semi-alicyclic or fully alicyclic polyimide resins, etc.
  • Patent Documents 1 to 3 These films are less colored and have transparency, but their mechanical strength is not as high as that of colored polyimide films. Colorlessness and transparency cannot always be maintained due to thermal decomposition or oxidation reaction.
  • Patent Document 4 a method of heat treatment while blowing a gas with a specified oxygen content has been proposed (Patent Document 4), but the production cost is high in an environment where the oxygen concentration is less than 18%, and industrial production is not possible. Extremely difficult.
  • composites of organic and inorganic materials are used to impart the properties of inorganic materials, such as high heat resistance, chemical resistance, and high surface hardness.
  • organic-inorganic hybridization techniques For example, it is known that CTE, Rth, and Tg can be improved while maintaining transparency by combining transparent polyimide and silica nanoparticles.
  • CTE, Rth, and Tg can be improved while maintaining transparency by combining transparent polyimide and silica nanoparticles.
  • the film becomes more rigid and brittle, resulting in a decrease in mechanical strength.
  • silsesquioxane represented by RSiO 3/2 can easily provide an organic-inorganic hybrid cured product by giving R a substituent that can react with an organic material.
  • Patent Document 5 Attempts have been made to improve heat resistance and workability by combining flexible silsesquioxane with polyimide. It is known that the charge transfer interaction between the imide portion of polyimide and silsesquioxane increases the thermal decomposition temperature (Non-Patent Document 1).
  • silsesquioxane composite polyimides since the flexible silsesquioxane structure reduces the rigidity of the polyimide, silsesquioxane composite polyimides usually exhibit relatively low elastic modulus and low Tg (Non-Patent Document 2). .
  • an object of the present invention is to provide a novel silsesquioxane compound and a method for producing the same, which are useful as a raw material for producing a polyimide film having improved toughness while maintaining other main properties. That's what it is.
  • the present invention includes the following contents.
  • R 2 is each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, Or represents an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • trialkoxysilanes a2 having no thiol group
  • a thiol group of the condensate B of said reactive group of dicarboxylic anhydride C having at least one reactive group selected from vinyl group, alkenyl group, cycloalkenyl group, alkynyl group, and acid chloride group
  • a silsesquioxane compound having a dicarboxylic anhydride group which has structural units represented by the following general formulas (1) and (2).
  • Q 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms
  • Q 2 is a single bond, a hydrocarbon group having 1 to 8 carbon atoms, an organic group in which one or more carbon atoms of the hydrocarbon group having 1 to 8 carbon atoms are substituted with oxygen, or a carbonyl group
  • X is carbon- a carbon bond, or an aliphatic ring having 4 to 10 carbon atoms, an aromatic ring having 6 to 10 carbon atoms, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur;
  • One or more of the hydrogens bonded to may be substituted with a hydrocarbon group, and 1.0 ⁇ m ⁇ 2.0 and 1.4 ⁇ n ⁇ 1.6.
  • Q 3 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms, and 1.4 ⁇ n ⁇ 1.6.
  • the molar ratio of the trialkoxysilanes a2 [moles of a2]/[moles of a1+moles of a2]), or the molar ratio of the structural units represented by the general formula (2) ([structural The silsesquioxane compound according to [1] or [2], wherein unit (2)]/[structural unit (1)+structural unit (2)]) is 0.1 or more and 0.7 or less.
  • Rx represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • R 1 Si(OR 2 ) 3 thiol group-containing trialkoxysilanes a1 represented by the general formula: R 1 Si(OR 2 ) 3 ; (Wherein, R 1 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • FIG. 1 is a 1 H NMR (CDCl 3 ) spectrum of SQ109 (PGMEA solution) used in Example 1.
  • 1 is a 1 H NMR (CDCl 3 ) spectrum of norbornenic anhydride used in Example 1.
  • FIG. Note that ⁇ 2.2 is a peak derived from acetone for washing instruments.
  • 1 is a 1 H NMR (CDCl 3 ) spectrum of a reaction mixture after reaction in Example 1.
  • FIG. 1 is a 1 H NMR (CDCl 3 ) spectrum of silsesquioxane SQ2 having an acid anhydride group obtained in Example 2.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ3 having an acid anhydride group obtained in Example 3.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ4 having an acid anhydride group obtained in Example 4.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ5 having an acid anhydride group obtained in Example 5.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ6 having an acid anhydride group obtained in Example 6.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ7 having an acid anhydride group obtained in Example 7.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ8 having an acid anhydride group obtained in Example 8.
  • FIG. 1 is a 1 H NMR (DMSO-d 6 ) spectrum of silsesquioxane SQ8 having an acid anhydride group obtained in Example 8.
  • the novel silsesquioxane compound A is a silsesquioxane compound having a dicarboxylic anhydride group (hereinafter sometimes simply referred to as an "acid anhydride group") and a thiol group-containing silsesquioxane compound.
  • a thiol group of condensate B and said reactive group of dicarboxylic anhydride C having at least one reactive group selected from vinyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, and acid chloride groups; is a silsesquioxane compound formed by the reaction of
  • the condensate B is a thiol group-containing trialkoxysilane a1 represented by the general formula: R 1 Si(OR 2 ) 3 , (Wherein, R 1 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • R 2 is each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, Or represents an aromatic hydrocarbon group having 6 to 8 carbon atoms.) It is a condensate B of trialkoxysilanes a2 having no thiol group.
  • the thiol group-containing trialkoxysilanes a1 and the trialkoxysilanes a2 both have three reactive alkoxy groups, so the structure of the resulting product has a three-dimensionally complicated structure. , it is not realistic to specify the entire structure by a chemical formula. For this reason, the product invention was specified in the form of manufacturing method limitation (product-by-process).
  • novel silsesquioxane compound A preferably has structural units represented by the following general formulas (1) and (2).
  • Q 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms
  • Q 2 is a single bond, a hydrocarbon group having 1 to 8 carbon atoms, an organic group in which one or more carbon atoms of the hydrocarbon group having 1 to 8 carbon atoms are substituted with oxygen, or a carbonyl group
  • X is carbon- a carbon bond, or an aliphatic ring having 4 to 10 carbon atoms, an aromatic ring having 6 to 10 carbon atoms, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur;
  • One or more of the hydrogens bonded to may be substituted with a hydrocarbon group, and 1.0 ⁇ m ⁇ 2.0 and 1.4 ⁇ n ⁇ 1.6.
  • novel silsesquioxane compound A is not limited to the product specified by the above manufacturing method limitation, and as two repeating units, structural units represented by the following general formulas (1) and (2) can be identified as having
  • the novel silsesquioxane compound A can be suitably produced, for example, by the production method of the present invention. That is, the production method of the present invention is a method for producing a silsesquioxane compound having a dicarboxylic anhydride group, comprising the following steps in order.
  • R 1 Si(OR 2 ) 3 thiol group-containing trialkoxysilanes a1 represented by the general formula: R 1 Si(OR 2 ) 3 ; (Wherein, R 1 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • thiol group-containing silsesquioxane compound (condensate B) and at least one reactive group selected from a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an acid chloride group It can also be obtained by reacting with a dicarboxylic anhydride C having
  • Condensate B is a condensate of thiol group-containing trialkoxysilanes a1 and trialkoxysilanes a2 having no thiol group.
  • Condensate B for example, an organic/inorganic hybrid resin Compoceran SQ (product name: SQ107 or SQ109, Arakawa Chemical Industries, Ltd.) can be used.
  • the condensate B synthesized by a method including the above 1st to 3rd steps can be used.
  • thiol group-containing trialkoxysilanes a1 represented by the general formula: R 1 Si(OR 2 ) 3 , trialkoxysilanes a2 having no thiol group, and water are combined with an acidic catalyst. It is a step of obtaining a reaction mixture x by hydrolyzing with
  • R 1 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms. represents an organic group substituted with a thiol group
  • R 2 is each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, Or represents an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • the limitation on the number of carbon atoms such as "1 to 8 carbon atoms" means the number of carbon atoms in the entire organic group including substituents.
  • R 1 has at least one thiol group and is a hydrocarbon group having 1 to 8 carbon atoms having a straight chain, branched chain, or aliphatic ring, or a hydrocarbon group. represents an aromatic hydrocarbon group having 6 to 8 carbon atoms which may be present.
  • R 1 is preferably a linear hydrocarbon group from the viewpoint of imparting flexibility to the polymer chain, and preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of enhancing heat resistance.
  • R 2 independently of each other may have a hydrogen atom, a linear or branched chain, or an aliphatic ring-containing hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group; Represents 6-8 aromatic hydrocarbon groups.
  • R 2 is preferably an alkyl group having 1 to 4 carbon atoms. A methyl group or an ethyl group is particularly preferred.
  • component (a1)) Specific examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercapto propyltributoxysilane, 1,4-dimercapto-2-(trimethoxysilyl)butane, 1,4-dimercapto-2-(triethoxysilyl)butane, 1,4-dimercapto-2-(tripropoxysilyl)butane, 1,4-dimercapto-2-(tributoxysilyl)butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyl tripropoxysilane, 2-mercaptomethyl-3-mercapto
  • Examples of trialkoxysilanes a2 having no thiol group include compounds represented by the general formula: R 3 Si(OR 2 ) 3 .
  • R 3 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms
  • R 2 is , each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • R 3 is a hydrocarbon group having 1 to 8 carbon atoms having a linear or branched chain or an aliphatic ring, or a hydrocarbon group having 6 to 8 carbon atoms which may have a hydrocarbon group. represents an aromatic hydrocarbon group.
  • R 2 is as described for component (a1), and may be the same as or different from R 2 in component (a1).
  • component (a2) examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • Component (a2) can be used either singly or in combination of two or more. By using these, the amount of thiol groups can be adjusted, so that the degree of cross-linking of the finally obtained polyimide can be adjusted and the proportion of the inorganic component in the polyimide can be increased.
  • the molar ratio of the trialkoxysilanes a2 in the alkoxysilanes is preferably 0.1 or more and 0.7 or less. It is more preferably 2 or more and 0.7 or less.
  • the larger the molar ratio the smaller the amount of thiol groups contained per molecule, and the smaller the molar ratio, the larger the amount of thiol groups.
  • the resulting polyimide chain is appropriately crosslinked, and the effect of improving physical properties is sufficient.
  • Condensate B which is a thiol group-containing silsesquioxane, can be obtained by using component (a1) and component (a2), hydrolyzing them, and then condensing them.
  • the alkoxy groups contained in the component (a1) and the component (a2) are converted into silanol groups by the hydrolysis reaction, and alcohol is produced as a by-product.
  • the amount of water required for the hydrolysis reaction is expressed as a molar ratio ([number of moles of water used for hydrolysis reaction]/[total number of moles of each alkoxy group contained in component (a1) and component (a2)]).
  • 0.4 to 10 are preferred. When this molar ratio is 0.4 or more and less than 0.5, some alkoxy groups will remain in the resulting thiol group-containing silsesquioxane, but adhesion to inorganic materials can be improved. Moreover, in the case of 0.5 to 10, substantially no alkoxy group remains in the thiol group-containing silsesquioxane to be obtained, and a thick film cured product can be easily produced.
  • dialkoxysilanes and/or tetraalkoxysilanes may be further used within a range that does not impair the effects of the present invention (for example, 50 mol % or less). It is possible.
  • any conventionally known acidic catalyst that can function as a hydrolysis catalyst can be used. However, since it is necessary to substantially remove the acid catalyst after the hydrolysis reaction, it is preferably one that can be easily removed. These include formic acid, which has a low boiling point and can be removed by vacuum, and solid acid catalysts, which can be easily removed by methods such as filtration.
  • solid acid catalysts examples include cation exchange resins, activated clay, and carbon-based solid acids.
  • cation exchange resins are preferable because they have high catalytic activity and are easily available.
  • As the cation exchange resin a strong acid type cation exchange resin and a weak acid type cation exchange resin can be used.
  • Diaion SK series, Diaion UBK series, Diaion PK series, Diaion HPK25/PCP series all product names of Mitsubishi Chemical Corporation
  • the type of ion-exchange resin to be used can be arbitrarily selected depending on the reaction rate, suppression of side reactions, etc., strongly acidic ion-exchange resins are particularly preferred from the viewpoint of reactivity.
  • the amount of the acid catalyst to be added is preferably 0.1 to 25 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass in total of the components (a1) and (a2).
  • it is 25 parts by mass or less, it tends to be easy to remove in a later step, which tends to be economically advantageous.
  • the amount is 0.1 parts by mass or more, the reaction can proceed appropriately, and there is a tendency that the reaction time does not become too long.
  • the reaction temperature and time can be arbitrarily set according to the reactivity of component (a1) and component (a2), but are usually about 0 to 100°C, preferably about 20 to 60°C for about 1 minute to 2 hours.
  • the hydrolysis reaction can be carried out in the presence or absence of a solvent, preferably without solvent.
  • a solvent the type of solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as used in the condensation reaction described below.
  • the second step is to remove the acidic catalyst from the reaction mixture x to obtain a reaction mixture y. That is, it is necessary to substantially remove the acid catalyst from the system after the hydrolysis reaction in the first step is completed. If not removed, the reaction does not proceed in the condensation reaction described later, the silanol group is not completely consumed, or the system gels due to an abnormal increase in the molecular weight. Oxane (condensate B) cannot be obtained.
  • the method for removing the acidic catalyst can be appropriately selected from various known methods depending on the catalyst used. For example, as described above, when formic acid is used, it can be easily removed by reducing pressure, and when a solid acid catalyst is used, it can be easily removed by a method such as filtration after completion of the condensation reaction.
  • by-product alcohol and excess water may be removed by a method such as decompression. Further, by diluting with the solvent used for the condensation reaction after removal, it is possible to facilitate the addition of the hydrolyzate in the subsequent condensation reaction.
  • the third step is a step of obtaining a condensate B having a thiol group by mixing and condensing a polar solvent containing a basic catalyst and the reaction mixture y.
  • a condensation reaction water is by-produced between the silanol groups, and alcohol is by-produced between the silanol groups and the alkoxy groups, forming siloxane bonds.
  • a conventionally known basic catalyst capable of functioning as a dehydration condensation catalyst can be arbitrarily used in the condensation reaction.
  • the basic catalyst preferably has a high basicity, and specific examples thereof include alkali salts such as sodium hydroxide (NaOH), potassium hydroxide (KOH) and calcium hydroxide (Ca(OH) 2 ); Organic amines such as 8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and ammonium hydroxides such as Any one of the exemplified compounds can be used alone or in combination as appropriate. Among the exemplified compounds, tetramethylammonium hydroxide is particularly preferred because of its high catalytic activity and easy availability. In addition, when these basic catalysts are used as an aqueous solution, the hydrolysis reaction proceeds even in the condensation reaction step. , should be adjusted accordingly.
  • alkali salts such as sodium hydroxide (NaOH), potassium hydroxide (KOH)
  • the amount of the basic catalyst to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass in total of component (a1) and component (a2). more preferred. If the amount of the basic catalyst added is 5 parts by mass or less, the cured product prepared using the obtained thiol group-containing silsesquioxane (condensate B) is difficult to color, and when removing the catalyst, it is removed. This tends to make the process of On the other hand, when the amount is 0.01 part by mass or more, the reaction can proceed appropriately, and there is a tendency that the reaction time does not become too long.
  • the reaction temperature can be arbitrarily set according to the reactivity of component (a1) and component (a2), but is usually about 40 to 150°C, preferably about 60 to 100°C.
  • the condensation reaction is preferably carried out in the presence of a polar solvent, and from the viewpoint of the stability of the obtained silsesquioxane compound A and its copolymer amic acid solution and the quality of the resulting film, a solvent such as toluene is used. It is more preferable not to contain a non-polar solvent.
  • polar solvent a polar solvent that exhibits compatibility with water is preferable, and glycol ethers are particularly preferable.
  • glycol ethers dialkyl glycol ether solvents are particularly preferred.
  • dialkyl glycol ether-based solvents compatible with water include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether.
  • Glycol ether acetate solvents such as propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate can also be used.
  • the condensation reaction can also be carried out by setting the reaction temperature to a polar solvent containing a dehydration condensation catalyst and sequentially adding a solution containing the hydrolyzate obtained in the hydrolysis reaction.
  • the method of addition can be appropriately selected from various known methods.
  • the time required for addition can be arbitrarily set depending on the reactivity of component (a1) and component (a2), but is usually about 30 minutes to 12 hours.
  • the total molar ratio of unreacted alkoxy groups ([total number of moles of unreacted alkoxy groups]/[total number of moles of each alkoxy group contained in component (a1) and component (a2)]) is 0.5. It is preferable to proceed so that it becomes 2 or less, and it is more preferable to make it substantially 0. When this molar ratio is more than 0 and 0.2 or less, some alkoxy groups will remain in the resulting thiol group-containing silsesquioxane (condensate B), but adhesion to inorganic materials is preferable in terms of improvement.
  • the condensation reaction is preferably carried out by diluting with a solvent so that the total concentration of component (a1) and component (a2) is about 2 to 80% by mass, more preferably 15 to 75% by mass. It is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction, because these can be distilled off from the reaction system. A concentration of 2% by mass or more is preferable because the thiol group-containing silsesquioxane (condensate B) contained in the obtained curable composition is sufficient. When it is 80% by mass or less, it becomes difficult to gel during the reaction, and the resulting condensate B tends to have an appropriate molecular weight.
  • the removal method can be appropriately selected from various known methods according to the catalyst used. For example, when tetramethylammonium hydroxide is used, it can be removed by adsorption and removal with a cation exchange resin after completion of the condensation reaction.
  • ⁇ Fourth step> the condensate B and a dicarboxylic anhydride C having at least one reactive group selected from a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an acid chloride group. This is the step of reacting.
  • a dicarboxylic anhydride having a functional group capable of reacting with a thiol group is used as the dicarboxylic anhydride C (hereinafter referred to as component (C)).
  • component (C) dicarboxylic anhydrides having vinyl groups, acryl groups, methacryl groups, allyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, or acid chloride groups
  • a dicarboxylic anhydride having a vinyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or an acid chloride group can be used.
  • the dicarboxylic anhydride C preferably has the following structure.
  • the following compounds and compounds having an acid chloride group are particularly preferred due to their high reactivity.
  • dicarboxylic anhydride C which has low reactivity, it is difficult to proceed the reaction completely with only UV light, so it is preferable to use an oxidation catalyst such as oxygen or iron chloride together.
  • phthalic anhydride compounds having an aromatic ring structure are desirable from the viewpoint of improving the heat resistance of the resulting polyimide and suppressing yellowing under high-temperature conditions.
  • Maleic anhydride and cyclohexanedicarboxylic anhydride having a cyclic structure are desirable in terms of enhancing colorless transparency.
  • thiol group-containing silsesquioxane (condensate B) and the dicarboxylic anhydride C
  • a thiol-ene reaction or a reaction between a thiol group and an acid chloride group can be used.
  • the reaction mechanism differs depending on the type of carbon-carbon double bond and the presence or absence of a radical polymerization initiator. That is, when a compound having a vinyl group or an allyl group with low radical polymerizability is used as component (C), only the en-thiol reaction proceeds, and the thiol group in condensate B and component (C) Carbon-carbon double bonds react at approximately 1:1 (molar ratio) and are preferred. On the other hand, when a compound having a highly radically polymerizable acrylic group or methacrylic group is used as the component (C), the carbon-carbon double bond in the component (C) is particularly affected when a radical polymerization initiator is used in combination.
  • the polymerization reaction also proceeds in parallel, and the thiol group in the condensate B and the carbon-carbon double bond in the component (C) react at a ratio of about 1: 1 to 100 (molar ratio), so the effect of the invention is You may not get enough.
  • the molar ratio [number of moles of thiol groups contained in condensate B]/[component (C) The number of moles of carbon-carbon double bonds contained in]) is preferably 0.9 to 2.5, more preferably 1.0.
  • this molar ratio is 0.9 or more, the carbon-carbon double bond is less likely to remain after UV curing, and the weather resistance tends to be improved. Moreover, when it is 2.5 or less, the crosslink density of the cured product becomes sufficient, and there is a tendency to improve the heat resistance.
  • an ultraviolet light source As a thiol-ene reaction initiator, an ultraviolet light source, an organic material, an inorganic material, or oxygen can be used.
  • an ultraviolet light source for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, or an ultraviolet LED can be used.
  • Usable initiators are not particularly limited, and conventionally known photo cationic initiators, photo radical initiators, oxidizing agents, etc. can be arbitrarily selected.
  • photocationic initiators include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate, etc., which are compounds that generate acid upon irradiation with ultraviolet rays. -6974, UVI-6990 (all trade names of Union Carbide Co., USA), Irgacure 264 (manufactured by BASF), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), and the like.
  • the amount of the cationic photopolymerization initiator to be used is usually about 10 parts by weight or less, preferably 1 to 5 parts by weight, per 100 parts by weight of the composition.
  • the photoradical initiator examples include Darocure 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all trade names manufactured by BASF), benzophenone, and the like, preferably about 5 parts by weight or less per 100 parts by weight of the composition. is 0.1 to 2 parts by mass.
  • the reaction can be accelerated by adding an oxidizing agent such as iron oxide or iron chloride.
  • an ultraviolet light source or oxygen for the reaction without using a photoreaction initiator or photosensitizer.
  • condensation B silanol group amount of the silsesquioxane
  • unreacted acid chloride groups may be copolymerized with polyamic acid to form polyamidoimide.
  • organic bases are N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidinone, imidazole, N-methylcaprolactam, imidazole, N,N-dimethylaniline and N,N-diethylaniline.
  • tertiary amines include pyridine, collidine, lutidine and triethylamine.
  • inorganic bases include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
  • a volatile base for substrate film applications that require high heat resistance and transparency, it is desirable to use a volatile base for the reaction. By removing hydrochloric acid by adding a base or heating the solution, gelation due to excessive reaction of silsesquioxane can be suppressed.
  • solvents used for the reaction Benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N- Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, imidazole, N-methylcaprolactam, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, hexamethylsulfolamide, cresol, pheno xylenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme, propylene glycol monomethyl ether acetate (
  • N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone as the main component of the organic solvent.
  • a poor solvent such as toluene or xylene may be used to the extent that the polyimide resin or its precursor does not precipitate.
  • the silsesquioxane compound A having an acid anhydride group obtained in the fourth step can be used as it is after the reaction. It can also be used as a powder.
  • silsesquioxane compound A Having an Acid Anhydride Group
  • the silsesquioxane compound A that can be obtained as described above preferably has structural units represented by the following general formulas (1) and (2). It is more preferred to have only the structural units represented.
  • Q 1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms
  • Q 2 is a single bond, a hydrocarbon group having 1 to 8 carbon atoms, an organic group in which one or more carbon atoms of the hydrocarbon group having 1 to 8 carbon atoms are substituted with oxygen, or a carbonyl group
  • X is carbon- a carbon bond, or an aliphatic ring having 4 to 10 carbon atoms, an aromatic ring having 6 to 10 carbon atoms, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur;
  • One or more of the hydrogens bonded to may be substituted with a hydrocarbon group, and 1.0 ⁇ m ⁇ 2.0 and 1.4 ⁇ n ⁇ 1.6.
  • Q 3 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 4 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms, and 1.4 ⁇ n ⁇ 1.6.
  • Q 1 in general formula (1) may have a hydrocarbon group having 1 to 8 carbon atoms having a straight chain, a branched chain, or an aliphatic ring, or a hydrocarbon group, It represents an aromatic hydrocarbon group having 6 to 8 carbon atoms.
  • Q1 is preferably a linear hydrocarbon group from the viewpoint of imparting flexibility to the polymer chain, and preferably an alicyclic hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of enhancing heat resistance.
  • Q 1 examples include a hydrocarbon group in which the Si atom and the S atom of the compound exemplified as the thiol group-containing trialkoxysilanes a1 are bonded, or an aromatic hydrocarbon group.
  • Q 2 is a hydrocarbon group having 1 to 8 carbon atoms having a single bond, a straight chain, or a branched chain, an oxygen-containing hydrocarbon group in which one or more of the carbon atoms is substituted with oxygen, or a carbonyl group .
  • Q2 is preferably a straight-chain hydrocarbon group from the viewpoint of imparting flexibility to the polymer chain, and is preferably a single bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group from the viewpoint of improving heat resistance.
  • X is a carbon-carbon bond, or an aliphatic ring having 4 to 10 carbon atoms, an aromatic ring having 6 to 10 carbon atoms, or a heterocyclic ring in which some of the carbon atoms constituting these are substituted with oxygen or sulfur It is a ring, and one or more of the hydrogen atoms attached thereto may be substituted with a hydrocarbon group.
  • X is preferably a carbon-carbon bond from the viewpoint of imparting flexibility to the polymer chain, and preferably a single bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group from the viewpoint of improving heat resistance.
  • X is an aromatic hydrocarbon group, it is preferable from the viewpoint of being able to improve heat resistance and suppress discoloration under high temperature conditions.
  • Q2 and X include reactive residues of compounds exemplified as dicarboxylic anhydride C, excluding dicarboxylic anhydride groups.
  • the following chemical formulas show examples in which X is a heterocyclic ring in which a part of carbon atoms constituting an aliphatic or aromatic ring is substituted with oxygen or sulfur.
  • n is 1.0 ⁇ m ⁇ 2.0, and m is preferably 1 from the viewpoint of small steric hindrance and high reactivity of the dicarboxylic anhydride group.
  • m is 1.0 ⁇ m ⁇ 2.0 (that is, other than an integer)
  • a component (a1) having one thiol group and a component having two thiol groups are used in combination.
  • n is 1.4 ⁇ n ⁇ 1.6, and from the viewpoint of forming a more uniform three-dimensional structure, n is preferably 1.5.
  • the reason why n is assumed to be other than 1.5 is to allow a small amount of not only trialkoxysilane but also dialkoxysilane and tetraalkoxysilane to be mixed in the raw material.
  • Q 3 in the general formula (2) may have a hydrocarbon group with 1 to 8 carbon atoms having a straight chain, a branched chain, or an aliphatic ring, or a hydrocarbon group with 6 carbon atoms. represents an aromatic hydrocarbon group of ⁇ 8.
  • Q3 is preferably a short-chain or branched-chain hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of suppressing crystallization and improving heat resistance.
  • Specific examples of Q3 include a hydrocarbon group or an aromatic hydrocarbon group that bonds to the Si atom of the compounds exemplified as the trialkoxysilanes a2.
  • the molar ratio of the structural units represented by the general formula (2) is preferably 0.1 or more and 0.7 or less, more preferably 0.2 or more and 0.7 or less.
  • the resulting polyimide chain is appropriately crosslinked, and the effect of improving physical properties is sufficient.
  • the number of acid anhydride groups (number of functional groups) per molecule of the silsesquioxane compound A is preferably 2-10, more preferably 2.5-6. When the number of functional groups is within this range, the resulting polyimide chain is moderately crosslinked, so that the effect of improving physical properties is sufficient.
  • the molecular weight of the silsesquioxane compound A is preferably 400-5000, more preferably 600-3000. When the molecular weight is within this range, the resulting polyimide is less likely to become non-uniform, and a uniform crosslinked structure is likely to be obtained.
  • silsesquioxane compound A having an acid anhydride group Since the silsesquioxane compound A has an acid anhydride group, it can be directly reacted with a compound having an amino group or a hydroxyl group, and since it produces a carboxyl group by reaction with water, it can be used with a wider variety of compounds. can be reacted.
  • a silsesquioxane compound having two or more acid anhydride groups serves as a monomer component of polyimide
  • a silsesquioxane compound having more than two acid anhydride groups serves as a copolymerization component to form a crosslinked structure in polyimide.
  • polyimide in general, there is a trade-off relationship between practical properties such as heat resistance and mechanical properties, and colorlessness (transparency or whiteness). In particular, toughness was improved while maintaining other properties. It would be desirable to have a method for making polyimide films.
  • a polyimide film can be obtained, for example, by including a step of synthesizing a polyamic acid solution, a step of forming a film from the polyamic acid solution, and a step of imidating the polyamic acid.
  • Carboxylic acids and diamines can be used as the polyamic acid monomer component to be combined with the silsesquioxane compound A having an acid anhydride group.
  • the carboxylic acids are not particularly limited, and include alicyclic tetracarboxylic anhydrides and aromatic tetracarboxylic anhydrides, tricarboxylic acids, and dicarboxylic acids that are commonly used in polyimide synthesis, polyamideimide synthesis, and polyamide synthesis. can be used.
  • Aromatics are preferred from the viewpoint of heat resistance, and alicyclics are preferred from the viewpoint of transparency. These may be used alone or in combination of two or more.
  • the alicyclic tetracarboxylic anhydrides used in the present invention include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and 1,2,3,4-cyclohexane.
  • Tetracarboxylic acid 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3′,4,4′-bicyclohexyltetracarboxylic acid, bicyclo[2,2,1]heptane-2,3,5,6 -tetracarboxylic acid, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetra carboxylic acids, tetrahydroanthracene-2,3,6,7-tetracarboxylic acid, tetradecahydro-1,4:5,8:9,10-trimethanoanthracene-2,3,6,7-tetracarboxylic acid, Decahydronaphthalene-2,3,6,7-tetracarboxylic acid, Decahydro-1,4:5,8-dimethanonaphthalene-2,3,6,7-tetracar
  • dianhydrides having two acid anhydride structures are preferred, particularly 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic An acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride is even more preferred. In addition, these may be used independently and may use 2 or more types together.
  • aromatic tetracarboxylic anhydrides used in the present invention include 4,4′-(2,2-hexafluoroisopropylidene)diphthalic acid, 4,4′-oxydiphthalic acid, bis(1,3-dioxo-1,3 -dihydro-2-benzofuran-5-carboxylic acid) 1,4-phenylene, bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl)benzene-1,4-dicarboxylate, 4,4′-[4,4′-(3-oxo-1,3-dihydro-2-benzofuran-1,1-diyl)bis(benzene-1,4-diyloxy)]dibenzene-1,2-dicarbon acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 4,4′-[(3-oxo-1,3-dihydro-2-benzofuran-1,1-
  • Tricarboxylic acids include aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, diphenylether-3,3′,4′-tricarboxylic acid, and diphenylsulfone-3,3′,4′-tricarboxylic acid.
  • acids or hydrogenated products of the above aromatic tricarboxylic acids such as hexahydrotrimellitic acid; Glycol bistrimellitate, and their monoanhydrides and esters.
  • monoanhydrides having one acid anhydride structure are preferred, and trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferred. In addition, these may be used individually and may be used in combination.
  • Dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-oxydibenzenecarboxylic acid, or the above aromatic dicarboxylic acids such as 1,6-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids and hydrogenated products thereof are preferred, and terephthalic acid, 1,6-cyclohexanedicarboxylic acid, and 4,4'-oxydibenzenecarboxylic acid are particularly preferred.
  • dicarboxylic acids may be used alone or in combination.
  • the diamines in the present invention are not particularly limited, and aromatic diamines, aliphatic diamines, and alicyclic diamines that are commonly used in polyimide synthesis, polyamideimide synthesis, and polyamide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferred, and from the viewpoint of transparency, alicyclic diamines are preferred. Diamines may be used alone or in combination of two or more.
  • aromatic diamines examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy)benzene, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′- Bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone , 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,
  • some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine may be substituted with a halogen atom, an alkyl or alkoxyl group having 1 to 3 carbon atoms, or a cyano group, and Some or all of the hydrogen atoms in the alkyl or alkoxyl groups of 1 to 3 may be substituted with halogen atoms.
  • Alicyclic diamines include, for example, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propyl cyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 9,10-bis(4-aminophenyl)adenine, 2,4-bis(4- aminophenyl)cyclobut
  • the molar content of the silsesquioxane compound A is 0.01 mol% or more, the effect of complexing is obtained, and when the molar content is 10.0 mol% or less, the gel of the polyamic acid solution This makes it difficult to cause quenching, and it is easy to obtain stability over time. Therefore, more preferably, the molar content is 0.1 to 5.0 mol %.
  • the polyamic acid solution may further contain optional components such as adhesion imparting agents, surfactants, leveling agents, antioxidants, UV absorbers, chemical imidizing agents, and colorants. In addition, it may further contain a filler or the like that can be contained in the polyimide film.
  • a uniform green film with a thickness of 1 to 100 ⁇ m can be obtained by casting a polyamic acid solution on a substrate and heating to volatilize the solvent.
  • Substrates used for forming a film by such a casting method include polymer films, glass plates, silicon rubber plates, metal plates, and the like.
  • polyethylene terephthalate film A4100 manufactured by Toyobo Co., Ltd.
  • a method of adjusting the concentration of the polyamic acid solution, a method of adjusting the gap between the coaters, and a method of repeatedly casting to obtain the desired film thickness are adopted.
  • a substrate having a desired film thickness can be produced.
  • the obtained green film is thermally imidized to obtain a polyimide film.
  • the polyimide film may have a single layer structure, or may have a laminated structure of two or more layers. From the viewpoint of the physical strength of the polyimide film and the ease of peeling from the inorganic substrate, it preferably has a lamination structure of two or more layers, and may have a lamination structure of three or more layers.
  • the physical properties (yellowness index, total light transmittance, haze, etc.) in the case where the polyimide film has a laminate structure of two or more layers refer to the values of the entire polyimide film unless otherwise specified.
  • the thickness of the polyimide film is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more.
  • the upper limit of the thickness of the polyimide film is not particularly limited, it is preferably 200 ⁇ m or less, more preferably 90 ⁇ m or less, and still more preferably 50 ⁇ m or less for use as a flexible electronic device. If it is too thin, it will be difficult to produce a film and transport it, and if it is too thick, it will be difficult to transport it with a roll.
  • the total light transmittance of the polyimide film in the present invention is preferably 75% or more, more preferably 85% or more, even more preferably 87% or more, and still more preferably 88% or more.
  • the upper limit of the total light transmittance of the polyimide film is not particularly limited, it is preferably 98% or less, more preferably 97% or less for use as a flexible electronic device.
  • the haze of the polyimide film in the present invention is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.5 or less, and still more preferably 0.3 or less.
  • the yellowness index of the polyimide film in the present invention (hereinafter also referred to as "yellow index" or “YI”) is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 5 or less.
  • the lower limit of the yellowness index of the polyimide film is not particularly limited, but in order to use it as a flexible electronic device, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. is.
  • the thickness direction retardation (Rth) of the polyimide film in the present invention is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and still more preferably 100 nm or less.
  • the lower limit of Rth of the polyimide film is not particularly limited, it is preferably 0.1 nm or more, more preferably 0.5 nm or more for use as a flexible electronic device.
  • the highly colorless and transparent polyimide film exhibiting the coefficient of linear expansion (CTE) of the present invention can also be realized by stretching in the process of forming the polyimide film.
  • a polyimide solution is applied to a polyimide film-producing support, dried to form a polyimide film containing a solvent of 1 to 50% by mass, and further on a polyimide film-producing support or peeled off from the support.
  • 1.5 to 4.0 times in the MD direction and 1.4 to 3.0 times in the TD direction in the process of drying the polyimide film containing 1 to 50% by mass of solvent at a high temperature.
  • thermoplastic polymer film is used as a support for producing a polyimide film, and after stretching the thermoplastic polymer film and the polyimide film at the same time, the stretched polyimide film is peeled off from the thermoplastic polymer film.
  • the average coefficient of linear expansion (CTE) between 50°C and 200°C of the polyimide film is preferably 40 ppm/K or less. More preferably, it is 35 ppm/K or less. Moreover, it is preferably -10 ppm/K or more, more preferably -5 ppm/K or more.
  • CTE is within the above range, the difference in coefficient of linear expansion with a general support (inorganic substrate) can be kept small, and the polyimide film and the inorganic substrate are peeled off even when subjected to a process of applying heat. You can avoid warping the whole body.
  • CTE is a factor representing reversible expansion and contraction with respect to temperature.
  • the method for measuring the CTE of the polyimide film is according to the method described in Examples.
  • the polyimide film may contain a filler.
  • the filler is not particularly limited, and includes silica, carbon, ceramics, etc. Among them, silica is preferable. These fillers may be used alone or in combination of two or more. Addition of the filler imparts projections to the surface of the polyimide film, thereby increasing the slipperiness of the polyimide film surface. Also, by adding a filler, the CTE and Rth of the polyimide film can be kept low.
  • the average particle size of the filler is preferably 1 nm or more, more preferably 5 nm or more. Also, it is preferably 1 ⁇ m or less, more preferably 500 nm or less, and still more preferably 100 nm or less.
  • the content of the filler in the polyimide film is preferably adjusted according to the average particle size of the filler.
  • the particle size of the filler is 30 nm or more, it is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, still more preferably 0.01 to 2% by mass, and particularly It is preferably 0.01 to 1% by mass.
  • the average particle diameter is less than 30 nm, it is preferably 0.01 to 50% by mass, more preferably 0.01 to 40% by mass, still more preferably 0.01 to 30% by mass, Particularly preferably, it is 0.01 to 20% by mass.
  • the method of adding a filler in a polyimide film is not particularly limited, but when preparing the above-mentioned polyamic acid (polyimide precursor) solution, or after preparation, a method of adding powder, a form of filler / solvent (slurry ), and the method of adding in the form of a slurry is particularly preferred.
  • the slurry is not particularly limited, but a slurry in which silica having an average particle size of 10 nm is dispersed in N,N-dimethylacetamide (DMAC) at a concentration of 20% by mass (for example, "Snowtex (registered trademark) DMAC manufactured by Nissan Chemical Industries, Ltd.
  • DMAC N,N-dimethylacetamide
  • the polyimide film may contain a coloring agent.
  • the YI of the film can be reduced.
  • the coloring agent include organic pigments, inorganic pigments, and dyes. Organic pigments and inorganic pigments are preferred in order to improve the heat resistance, reliability, and light resistance of the colored film.
  • organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; Anthraquinone pigments such as pyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; quinophthalone-based pigments; threne-based pigments; and metal complex-based pigments.
  • diketopyrrolopyrrole pigments such as azo, disazo and polyazo
  • phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine
  • Anthraquinone pigments such as pyrimidine, flavan
  • inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum.
  • Dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.
  • the tensile breaking strength of the polyimide film is preferably 60 MPa or more, more preferably 120 MPa or more, and still more preferably 160 MPa or more. Although the upper limit of the tensile strength at break is not particularly limited, it is practically less than about 1000 MPa. When the tensile strength at break is 60 MPa or more, it is possible to prevent the polyimide film from breaking when it is peeled off from the inorganic substrate.
  • the method for measuring the tensile strength at break of the polyimide film is according to the method described in Examples.
  • the tensile elongation at break of the polyimide film is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more. When the tensile elongation at break is 5% or more, the handleability is excellent.
  • the method for measuring the tensile elongation at break of the polyimide film is according to the method described in Examples.
  • the tensile modulus of the polyimide film is preferably 2 GPa or more, more preferably 3 GPa or more, and still more preferably 4 GPa or more.
  • the tensile modulus is preferably 20 GPa or less, more preferably 12 GPa or less, and even more preferably 10 GPa or less.
  • the polyimide film can be used as a flexible film.
  • the method for measuring the tensile modulus of the polyimide film is according to the method described in Examples.
  • the polyimide film is preferably obtained in the form of being wound as a long polyimide film having a width of 300 mm or more and a length of 10 m or more at the time of its production. Morphology is more preferred. When the polyimide film is wound into a roll, the polyimide film wound into a roll can be easily transported.
  • a lubricant particles having a particle diameter of about 10 to 1000 nm is added and contained in the polyimide film in an amount of about 0.03 to 3% by mass. It is preferable to provide the surface of the polyimide film with fine irregularities to ensure slipperiness.
  • the CTE difference between the first polyimide film layer in contact with the inorganic substrate and the second polyimide film layer adjacent to the first polyimide film without contacting the inorganic substrate is preferably 40 ppm/K or less. , more preferably 30 ppm/K or less, and still more preferably 15 ppm/K or less.
  • the thickest layer of the second polyimide film has a thickness within the above range.
  • the polyimide film has a symmetrical structure in the film thickness direction because warping is less likely to occur.
  • the first polyimide film layer in contact with the inorganic substrate and the second polyimide film layer adjacent to the first polyimide film layer (hereinafter simply referred to as "second The thickness of the mixture at the interface with the second polyimide film layer)) is less than the sum of the thickness of one layer of the first polyimide film layer and the thickness of one layer of the second polyimide film layer.
  • second The thickness of the mixture at the interface with the second polyimide film layer is less than the sum of the thickness of one layer of the first polyimide film layer and the thickness of one layer of the second polyimide film layer.
  • the lower limit is not particularly limited, but industrially, there is no problem if it is 10 nm or more, and it may be 20 nm or more.
  • Means for forming a layer with less mixing is not particularly limited, but rather than simultaneously producing two layers of the first polyimide film layer and the second polyimide film layer by solution casting, the first polyimide film layer or It is preferable to fabricate any one layer of the second polyimide film layer and fabricate the next layer after passing through the heating step. It includes both the intermediate stage and the completed heating process. It is better to make the next layer after the heating process is completed, but the finished film surface often has already lost reactivity, and since there are few functional groups on the surface, it is difficult to separate the two layers. Poor adhesive strength may cause problems in practical use. Therefore, even if there is little mixing, it is desirable to have an interface where the mixing occurs at a thickness of 10 nm or more.
  • simultaneous coating with a T-die capable of simultaneous ejection of two layers, sequential coating in which one layer is coated and then the next layer is coated, and one layer is coated and then dried.
  • various existing coating methods and multi-layering techniques can be appropriately incorporated.
  • ⁇ Thickness measurement of polyimide film> The thickness of the film was measured using a micrometer (Millitron 1245D manufactured by Fineruff Co.). In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.
  • Total light transmittance The total light transmittance (TT) of the film was measured using a Hazemeter (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.
  • ⁇ Haze> The haze of the film was measured using a Hazemeter (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. In addition, the same measurement was performed 3 times and the arithmetic mean value was adopted.
  • YI 100 ⁇ (1.28X ⁇ 1.06Z)/Y ⁇ Glass transition temperature (Tg), coefficient of linear expansion (CTE)> It was measured using a TMA (TMA4000S, BRUKER AXIS). The film was cut into strips of width 15 mm ⁇ length 2 mm, and set in the device with a chuck distance of 10 mm and a load of 5 gf. In an argon atmosphere, the temperature was raised to 250°C at a rate of 20°C/min, and then lowered to 30°C at a rate of 5°C/min. After that, the temperature was raised at a rate of 10° C./min up to a temperature (Td1-20° C.) at which thermal decomposition does not occur. The CTE was calculated from the slope in the 200° C. to 50° C. interval during the temperature decrease, and the inflection point during the second temperature increase was defined as Tg.
  • Example 1 Synthesis of silsesquioxane SQ1 having an acid anhydride group
  • thiol group-containing silsesquioxane solution manufactured by Arakawa Chemical Industries, Ltd., Compoceran SQ-109
  • 10 g thiol group amount 16.7 mmol
  • norbornenic anhydride 2.74 g (16.7 mmol) were placed in a reaction vessel.
  • ultraviolet light spot Cure SP-11, manufactured by USHIO
  • NMR and IR measurements confirmed that the thiol group and norbornene were reacting.
  • the resulting solution was filtered through a PTFE filter (pore size 10 ⁇ m) and then used for synthesizing a polyamic acid solution described later (the same applies to SQ3 to SQ9).
  • the molar ratio and the average number of thiol groups per molecule were calculated as follows.
  • the molar ratio of methyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane was calculated from the integral ratio of .
  • FIGS. 1 HNMR CDCl 3
  • SQ-109 PGMEA solution in FIG. 2, PGMEA in FIG. 2, norbornenic anhydride in FIG. 3, and reaction mixture after reaction in FIG. 4
  • the peaks ( ⁇ 6.3, etc.) derived from the double bond of norbornenic anhydride disappeared, suggesting that the reaction between the thiol group and the double bond proceeded.
  • Example 2 Synthesis of silsesquioxane SQ2 having an acid anhydride group
  • Thiol group-containing silsesquioxane solution manufactured by Arakawa Chemical Industries, Ltd., Compoceran SQ-109
  • 10 g thiol group amount 16.7 mmol
  • norbornenic anhydride 2.74 g (16.7 mmol)
  • iron (III) chloride 1 mg was put into a reaction vessel and stirred for 10 minutes to obtain silsesquioxane SQ2 having an acid anhydride group as a pale yellow solution (yellow coloration is considered to be derived from iron chloride).
  • NMR and IR measurements confirmed that the thiol group and norbornene were reacting.
  • FIG. 5 shows the 1 HNMR (CDCl 3 ) spectrum of the reaction mixture after the reaction as a result of NMR measurement.
  • the peaks ( ⁇ 6.3, etc.) derived from the double bond of norbornenic anhydride disappeared, suggesting that the reaction between the thiol group and the double bond proceeded.
  • Example 3 Synthesis of silsesquioxane SQ3 having an acid anhydride group
  • 20 g of the solution of the thiol group-containing silsesquioxane compound 1 obtained in Synthesis Example 1 (thiol group amount 97.0 mmol), 15.9 g (97.0 mmol) of norbornenic anhydride, and 10.0 g of PGMEA were placed in a reaction vessel.
  • ultraviolet light spot Cure SP-11, manufactured by USHIO
  • NMR and IR measurements confirmed that the thiol group and norbornene were reacting.
  • Example 4 Synthesis of silsesquioxane SQ4 having an acid anhydride group
  • 20 g of the solution of the thiol group-containing silsesquioxane compound 2 obtained in Synthesis Example 2 (thiol group amount 77.9 mmol), norbornenic anhydride 12.8 g (77.9 mmol), and PGMEA 10.0 g were placed in a reaction vessel.
  • ultraviolet light spot Cure SP-11, manufactured by USHIO
  • NMR and IR measurements confirmed that the thiol group and norbornene were reacting.
  • Example 5 Synthesis of silsesquioxane SQ5 having an acid anhydride group
  • 20 g of the solution of the thiol group-containing silsesquioxane compound 3 obtained in Synthesis Example 3 (thiol group amount 54.5 mmol), 8.95 g (54.5 mmol) of 5-norbornene-2,3-dicarboxylic anhydride, 10.0 g of PGMEA was placed in a reaction vessel and irradiated with ultraviolet light (Spot Cure SP-11, manufactured by USHIO) for 20 minutes while stirring to obtain silsesquioxane SQ5 having an acid anhydride group as a colorless transparent solution.
  • Spot Cure SP-11 manufactured by USHIO
  • Example 6 Synthesis of silsesquioxane SQ6 having an acid anhydride group
  • a thiol group-containing trialkoxysilane solution manufactured by Arakawa Chemical Industries, Ltd., Compoceran SQ-109
  • 6 g thiol group amount 10.0 mmol
  • allylsuccinic anhydride 1.40 g (10.0 mmol) were placed in a reaction vessel,
  • UV light MAX-303, manufactured by Asahi Spectrosco Co., Ltd.
  • Example 7 Synthesis of silsesquioxane SQ7 having an acid anhydride group
  • Thiol group-containing trialkoxysilane solution manufactured by Arakawa Chemical Industries, Ltd., Compoceran SQ-109
  • 6 g thiol group amount 10.0 mmol
  • exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid 1.66 g (10.0 mmol) of the anhydride is placed in a reaction vessel and irradiated with ultraviolet light (MAX-303, manufactured by Asahi Spectrosco Co., Ltd.) for 20 minutes while stirring to form a colorless and transparent solution having an acid anhydride group.
  • Sesquioxane SQ7 was obtained.
  • NMR and IR measurements confirmed that the thiol group and exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride were reacted.
  • Example 8 Synthesis of silsesquioxane SQ8 having an acid anhydride group
  • Thiol group-containing trialkoxysilane solution Compoceran SQ-109, manufactured by Arakawa Chemical Industries, Ltd.
  • 3 g thiol group amount 5.0 mmol
  • 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydride 0.94 g (5.0 mmol) of the compound and ⁇ -butyrolactone (5 mL) were placed in a reaction vessel and irradiated with ultraviolet light (MAX-303, manufactured by Asahi Spectrosco Co., Ltd.) for 20 minutes while stirring to give an acid as a yellow transparent solution.
  • MAX-303 ultraviolet light
  • Example 9 Synthesis of silsesquioxane SQ9 having an acid anhydride group
  • a thiol group-containing trialkoxysilane solution (Compoceran SQ-109, manufactured by Arakawa Chemical Industries, Ltd.) 6 g (thiol group amount 10.0 mmol) was placed in a reaction vessel, and 2.10 g of trimellitic anhydride chloride (10.0 mmol) was added with stirring. 0 mmol) was added slowly.
  • silsesquioxane SQ9 having an acid anhydride group was obtained as a colorless transparent solution. NMR and IR measurements confirmed that the thiol group and the acid chloride group were reacting.
  • the molar ratio of SQ1 is a value calculated based on the divalent acid anhydride group. Specifically, the total number of moles of the unit structure derived from the silsesquioxane compound A is It is calculated as a number divided by the total number of groups and doubled (the same applies to the following molar ratios).
  • the polyamic acid solutions obtained in the above production examples and comparative production examples were made into films by the following methods, and their optical properties, thermal properties, and mechanical properties were measured.
  • Polyamic acid solution A was applied onto a polyester film (A4100, Toyobo product) using a casting applicator and heated at 100° C. for 18 minutes in a nitrogen atmosphere.
  • the resulting green film was cut with a cutter, peeled off from the polyester film, and fixed to a metal frame.
  • the temperature was increased stepwise at a rate of 10°C/min, and the temperature was increased by heating sequentially at 200°C x 10 minutes, 250°C x 10 minutes, 300°C x 10 minutes, and 350°C x 10 minutes. imidization was performed. After standing to cool, the polyimide film was obtained by removing from the metal frame.
  • a polyimide film was obtained in the same manner as in Production Example 1 except that polyamic acid solutions A1, B1, B4, B5, B6, C1, C2, C3, and D1 were used instead of polyamic acid solution A in Production Example 1. rice field. Table 1 shows the components used at that time and the evaluation results.
  • the polyimide films containing 1 mol % of SQ1 in the structure have the same composition except that they do not contain SQ1 (Comparative Production Example 1 , 2, 6, and 9), the total light transmittance, haze, yellow index, Tg, and CTE are substantially the same, and the tensile product is increased.
  • Production Examples 3a to 3e, Comparative Production Example 6, Comparative Production Example 7, and Comparative Production Example 8 have an improved tensile product compared to Comparative Production Example 6, but the Comparative Production Example 7.
  • Comparative Production Example 8 had a tensile product comparable to that of Comparative Production Example 6.
  • Production Example 3a, Comparative Production Example 7, and Comparative Production Example 8 are all polyimides containing silsesquioxane having the same acid anhydride group (norbornenic anhydride) in the structure, but were used in Production Example 3a.
  • SQ1 contains a thioether group between the acid anhydride group and the silsesquioxane structure
  • SQN1 and SQN2 used in Comparative Production Examples 7 and 8 do not contain a thioether group. It was suggested that copolymerization of silsesquioxanes containing thioether groups in the structure is useful for improving the tensile product.
  • Application example 1 First, the polyimide film obtained in Production Example 3a (PMDA/TFMB/SQ1) was cut into a rectangle of 360 mm ⁇ 460 mm.
  • UV/O 3 irradiation was performed for 3 minutes using a UV/O 3 irradiator (SKR1102N-03 manufactured by LAN Technical Co., Ltd.) for film surface treatment. At this time, the distance between the UV/O3 lamp and the film was 30 mm.
  • the glass substrate coated with the silane coupling agent is set on a roll laminator equipped with a silicone rubber roller. got wet.
  • the surface-treated surface of the polyimide film subjected to the surface treatment is superimposed so as to face the silane coupling agent-coated surface of the glass substrate, that is, the surface wetted with pure water, and the polyimide is sequentially applied from one side of the glass substrate with a rotating roll.
  • a temporary laminate was obtained by laminating the glass substrate and the polyimide film by applying pressure while extruding pure water between the film and the glass substrate.
  • the laminator used was a laminator with an effective roll width of 650 mm manufactured by MCK. It was 55% RH.
  • the resulting temporary laminate was heat-treated in a clean oven at 200°C for 10 minutes to obtain a laminate consisting of a polyimide film and a glass substrate.
  • a tungsten film (thickness: 75 nm) was formed on the polyimide film surface of the obtained laminate by the following steps, and a silicon oxide film (thickness: 150 nm) was laminated as an insulating film without being exposed to the atmosphere.
  • a silicon oxynitride film (thickness: 100 nm) serving as a base insulating film was formed by plasma CVD, and an amorphous silicon film (thickness: 54 nm) was laminated without being exposed to the atmosphere.
  • a TFT element was fabricated using the obtained amorphous silicon film.
  • an amorphous silicon thin film is patterned to form a silicon region of a predetermined shape, and then a gate insulating film is formed, a gate electrode is formed, an active region is doped to form a source region or a drain region, and an interlayer insulating film is formed.
  • formation of a source electrode and a drain electrode, and activation treatment were performed to fabricate an array of P-channel TFTs.
  • a UV-YAG laser is used to burn off the polyimide film part along the inside of the outer circumference of the TFT array by about 0.5 mm. got an array. The peeling was possible with very little force, and the peeling was possible without damaging the TFT. The resulting flexible TFT array was wound around a round bar of 5 mm in diameter without deterioration in performance and maintained good characteristics.
  • the polyimide film of the present invention has good mechanical properties while maintaining the same level of optical properties and thermal properties as compared to the case where the silsesquioxane compound is not contained. .
  • the polyimide film of the present invention has excellent optical properties, colorless transparency, excellent mechanical properties, and exhibits a relatively low CTE. After that, various electronic device processing is performed on the film, and finally the film is separated from the inorganic substrate, whereby a flexible electronic device can be produced.

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Abstract

L'invention concerne un composé silsesquioxane possédant un groupe anhydride d'acide dicarboxylique, qui est constitué par réaction : d'un groupe thiol d'un produit de condensation (B) de trialcoxysilanes à teneur en groupe thiol (a1) représentés par la formule générale Ｒ１Ｓｉ（ＯＲ２）３ (Dans la formule, Ｒ１ représente un groupe organique dans lequel au moins un hydrogène d'un groupe hydrocarbure aliphatique de 1 à 8 atomes de carbone, ou similaire, est substitué par un groupe thiol, et Ｒ２ représentent, indépendamment les uns des autres, un atome d'hydrogène, un groupe hydrocarbure aliphatique de 1 à 8 atomes de carbone, ou similaire.), et de trialcoxysilanes (a2) ne possédant pas de groupe thiol ; et d'un groupe réactif d'un anhydride d'acide dicarboxylique (C) possédant ledit groupe réactif constitué d'un groupe vinyle, d'un groupe alcényle, d'un groupe cycloalcényle, d'un groupe alcynyle ou d'un groupe chlorure d'acide.
PCT/JP2022/025227 2021-06-29 2022-06-24 Composé silsesquioxane, et procédé de fabrication de celui-ci WO2023276864A1 (fr)

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CN116285863A (zh) * 2023-02-17 2023-06-23 深圳市聚芯源新材料技术有限公司 一种低介电常数的复合工程塑料及其制备方法

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JPH07196797A (ja) * 1993-12-28 1995-08-01 Toyobo Co Ltd ポリアミドイミド樹脂およびその製造方法
JP2005537318A (ja) * 2002-08-30 2005-12-08 ユニヴァーシティ オブ ピッツバーグ Ｎ−ビニルホルムアミドの合成
JP2007001174A (ja) * 2005-06-24 2007-01-11 Toyobo Co Ltd 多層ポリイミドフィルム
WO2008146637A1 (fr) * 2007-05-24 2008-12-04 Mitsubishi Gas Chemical Company, Inc. Procédé et appareil de production de film de résine transparent incolore
WO2010140551A1 (fr) * 2009-06-02 2010-12-09 日産化学工業株式会社 Composition pour la formation d'un film de sous-couche de réserve contenant du silicium ayant une liaison sulfure
WO2020175337A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image
JP2020184010A (ja) * 2019-05-07 2020-11-12 Jsr株式会社 感放射線性組成物、表示装置用絶縁膜、表示装置、表示装置用絶縁膜の形成方法、及びシルセスキオキサン

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Publication number Priority date Publication date Assignee Title
JPS49114663A (fr) * 1973-02-16 1974-11-01
JPH07196797A (ja) * 1993-12-28 1995-08-01 Toyobo Co Ltd ポリアミドイミド樹脂およびその製造方法
JP2005537318A (ja) * 2002-08-30 2005-12-08 ユニヴァーシティ オブ ピッツバーグ Ｎ−ビニルホルムアミドの合成
JP2007001174A (ja) * 2005-06-24 2007-01-11 Toyobo Co Ltd 多層ポリイミドフィルム
WO2008146637A1 (fr) * 2007-05-24 2008-12-04 Mitsubishi Gas Chemical Company, Inc. Procédé et appareil de production de film de résine transparent incolore
WO2010140551A1 (fr) * 2009-06-02 2010-12-09 日産化学工業株式会社 Composition pour la formation d'un film de sous-couche de réserve contenant du silicium ayant une liaison sulfure
WO2020175337A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image
JP2020184010A (ja) * 2019-05-07 2020-11-12 Jsr株式会社 感放射線性組成物、表示装置用絶縁膜、表示装置、表示装置用絶縁膜の形成方法、及びシルセスキオキサン

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285863A (zh) * 2023-02-17 2023-06-23 深圳市聚芯源新材料技术有限公司 一种低介电常数的复合工程塑料及其制备方法
CN116285863B (zh) * 2023-02-17 2024-01-23 深圳市聚芯源新材料技术有限公司 一种低介电常数的复合工程塑料及其制备方法

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